Polyurethane plastic compositions containing flame retardants

ABSTRACT

PLASTIC COMPOSITIONS CONTAINING POLYURETHANES AND BISPHENOXY COMPOUNDS HAVING THE FORMULA   (((Z)M,(AI)-PHENYL)-O-R-O-),(Z)M&#39;&#39;,(A)I&#39;&#39;-BENZENE   WHEREIN Z IS BROMINE OR CHLORINE M AND M&#39;&#39; ARE INTEGER HAVING A VALUE OF 1-5, I AND I&#39;&#39; ARE INTEGERS HAVING A VALUE OF 0-2, R IS HEREIN DEFINED AND A IS CYANO, NITRO LOWER ALKOXY, LOWER ALKYL, FLUORINE, DIALKYLAMINO, PHENYL, HALO-PHENYL, BENZYL OR HALO-BENZYL.

United States Patent 05cc US. Cl. 260-45.9 R 14 Claims ABSTRACT OF THEDISCLOSURE Plastic compositions containing polyurethanes and bisphenoxycompounds having the formula wherein Z is bromine or chlorine, m and m'are integers having a value of 1-5, 1' and i' are integers having avalue of -2, R is herein defined and A is cyano, nitro, lower alkoxy,lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl orhalo-benzyl.

This application is a continuation-in-part of copending application Ser.No. 260,240, filed June 6, 1972, and now abandoned. The entirespecification of this case, Ser. No. 260,240, is to be considered asincorporated herein by reference.

The prior art considered in conjunction with the preparation of thisapplication is as follows: US. 2,130,990; US. 2,186,367; US. 2,329,033;US. 3,666,692; US. 3,686,320; U.S. 3,658,634; German Pat. No. 1,139,636;German Pat. No. 2,054,522; Japanese Pat. No. (72) 14,500 as cited inVolume 77, Chemical Abstracts, column 153737k (1972); ChemicalAbstracts, Volume 13, column 448 Chemical Abstracts, Volume 31, column7045 and Journal of the Chemical Society, pages 2972- 2976 (1963). Allof these publications are to be considered as incorporated herein byreference.

The present invention relates to plastic compositions containingpolyurethanes (including, without limitation, rigid foams, semi-rigidfoams, flexible foams, rubbers, and adhesives). More specifically, thepresent invention covers plastic compositions containing polyurethanesand certain bis-phenoxy compounds (hereinafter defined) as flameretardants for said plastic compositions.

Polyurethanes and utility thereof are known in the art as exemplified byPolyurethanes, B. A. Dombrow (Reinhold Plastics Applications Series),Reinhold Publishing Corporation, New York, 1965 and Modern PlasticsEncyclopedia 1972-1973, Vol. 49: No. 10A, October 1972, pages 110, 112,162, 276, 278, 279, 282 and 283 and which publications are in totoincorporated herein by reference.

The need for flame retarding polyurethanes has also been recognized inthe art as exemplified by US. 3,347,- 822 and Modern PlasticsEncyclopedia, ibid, pages 222, 456-458 and which publications are intoto incorporated herein by reference.

The resultant disadvantages in the utilization of various prior artmaterials as flame retardants for polyurethanes include, withoutlimitation, factors such as thermal migration, heat instability, lightinstability, non-biodegradable, toxicity, discoloration and the largeamounts employed in order to be effective.

Thus, there is always a demand for a material which will function as aflame retardant in polyurethanes, and concurrently will not, byincorporation therein, adversely 3,835,092 Patented Sept. 10, 1974effect the chemical and/or physical and/or mechanical properties of theresultant polyurethane plastic composition.

The prior art problem of providing a flame retarded polyurethanecomposition having desired chemical, physical and mechanical propertieshas now been substantially solved by the present invention and theabove-described disadvantages substantially overcome.

Accordingly, one of the main objects of the present invention is toprovide polyurethane plastic compositions which are flame retarded.

Another object of the present invention is to provide a material forpolyurethane plastic compositions which will not substantially adverselyeffect the chemical and/or physical and/or mechanical properties of saidcompositions.

A further object of the present invention is to provide a flameretardant which is economic and easy to incorporate into polyurethaneplastics without being degraded or decomposed as a result of blending orprocessing operations.

It has been found that the foregoing objects can be obtained by theincorporation of a new class of bis phenoxy compounds in polyurethane tosubsequently provide flame retarded compositions which exhibitoutstanding chemical, physical and mechanical properties.

This bis-phenoxy compounds used in the present invention compositionhave the formula:

In Formula I above, Z is bromine or chlorine, m and m are integers eachindependently having a value of 1-5; i and i are integers eachindependently having a value of 0-2; A is from the group, cyano (CN),nitro (NO lower alkoxy (e.g. -OCH 0C H lower alkyl (e.g. CH C H C H C Hfluorine, dialkylamino e.g. 3)z, z 5)2 P y e s), halophenyl, benzyl (CHC H and halo-benzyl; and R is from the group (a) CH:-CH(OH)CH;

(b) CH -CH(CH OH)-CH where w=1-6 (d) Xn CH@CH1 where X=H, Cl, Br

(f) CHa-OH where S=saturated ring.

3 4 In Formula I, i-i-m or i+m' is not greater than 5. Illustrative (butwithout limitation) of some of the It i to be understood th t ll f thcompounds fallpresent invention bis-phenoxy compounds are shown beingwithin the above Formula I and as heretofore defined 10w:

are generically described herein as bis-phenoxy com- (I) p 5 z S -OROC ZI The bis-phenoxy compounds are found to be oompatible m O m with andeffective additives for various polymeric systems h exemplary d fi iti fA, Z, R, i" m and are to make the resultant polymer flame retardant.listed in Table I.

TABLE I Compound No. Z m m A R CHzCH(OH) CH CHzCH(OH)CHz CH2CH(OH) CHCHQGH (OH) OH: CH2CH(OH) CH CH2CH(OH) CH2 CH2CH(OH) CH2 CHZCH (DEUCE;CHgCH (OH) CH2 CHECH (O H) CH2 CHflOH (OH) CH: CHaCEKOH) CH:

CHQO CH: CHgO CH2 CH2OOH2 (CH2) 4O (CH2)4 C1120 CH2 (01193 2b CHzO CH5OHzOCHz CHBO CH2 1920 CH2 CHzOCHz (OH2)2O (CH2): CHzO CH3 OHZOCHB CH OCH2 CH2O CH2 CHZO CH2NmwlotototomtoN60towwwuiowumihmmwnhmwwwwmmumwmNNMMMwv-neetbnowuthtewwmMMMwwzowwMwMmzoHuwm-mwmihwwwxommlonwmmwmeamNweetowtowzerowmronewwe:totweetoweeteweewioteuwmromeawnmueewuHema-wweawzeceeomrewwwmreeamutowwzowwwmteeecemwceunewwieietowrotomwww TABLE I-Continued Z mm Compound No.

m m m m m m u u m n u h a u n B u u h H m m H u m am h F I H mmmn m a va m m m an. im a. I a? MPH nflmom mm H mmHH m N u m N mHiooH Hi I QCOmwfiH H N moon m "CNOC 00 h C NCCOCC C n C C ONOO C ONOOC NGOCOC C CNOCCO m F m FIIIFI F F F m F 43324311232 22222223324 3324332431122223222222233243324311 In general, this bis-phenoxy compounds areprepared anol, ethanol, iso-propyl alcohol, butvl alcohol and glybyreacting a halogenated phenol 'With a halogenated cols), or aqueoussolvents (e.g. water, a mixture of Water alkane at elevated temperaturesin the presence of a basic and alcohol and a mixture of water andketone) can be material such as alkali metal hydroxides, carbonates, bi-70 employed. The desired end product i.e. the bis-phenoxy i compound,can be recovered from the reaction mass via various methods such asdistillation or crystallization. Where the end product requires recoveryvia crystallization, various aromatic solvents such as benzene, toluene,tone, and methyl iso-butyl ketone), alcohols (e.g. meth- 75 xylenedichlorobenzene and the like can be used.

carbonates, oxides and hydrides. The preferred alkal metals arepotassium and sodium. Where one desires to increase, for example, easeof handling the reaction mass, solvents such as ketones (e.g. acetone,methyl ethyl ke- Specifically, the bis-phenoxy compounds are preparedaccording to the following reactions:

A: 2- @011 XRX (11) (III) At Av 2HX zm@-oR- zm- In the above reaction, Xis halogen, preferably chlorine and R is the same as defined herein.Where m and m and i and i are different integers, then equivalent molarportions of the particular halogenated phenol are used with equivalentportions of dissimilar halogenated phenol.

The above reaction is conducted at temperatures ranging from thefreezing point of the initial reaction mass to the boiling pointthereof. Preferably the temperatures are from about 40 C. to about 200C. and more preferably from about 50 C. to about 175 C. It is to beunderstood that the reaction can be conducted under sub-atmospheric-(e.g. atmospheres), atmospheric of super-atmospheric (e.g. 1.5-10atmospheres) pressure. Preferably, the reaction is carried out atatmospheric pressure.

The above-described processes can be carried out with conventional,readily available chemical processing equipment. For example, aconventional glass-lined vessel provided with heat transfer means, areflux condenser and a mechanical stirrer can be advantageously utilizedin practicing any of the preferred embodiments of the inventiondescribed in the examples set forth herein.

The amount of bis-phenoxy compound employed in the present inventioncompositions is any quantity which will effectively render thepolyurethane containing composition flame retardant. In general, theamount used is from about 1% to 25% by weight, based on the total weightof the composition. Preferably, the amount employed is from about toabout 20% by weight. It is to be understood that any amount can be usedas long as it does not substantially adversely eifect the chemical and/or physical and/or mechanical properties of the end polymer composition.The amount utilized, however, is such amount which achieves theobjectives described herein.

It is to be understood that the term polyurethanes as used herein meanspolymers containing repeated urethane linkages where R is aromatic oraliphatic group. These polymers are generally made by reacting apolyisocyanate with a compound having a plurality of active hydrogens(i.e. a compound having active hydrogen and which gives a positiveZerewitinoff test).

Thus the polyurethanes used in the present invention compositions is anypolyurethane herein defined and which one so desires to flame retard. Itis to be understood that the polyurethanes used can be a virginmaterial, i.e. substantially free of additives such as stabilizers,plasticizers, dyes, pigments, fillers, and the like, or thepolyurethanes can have additives (such as those mentioned and describedherein) already contained therein or added concurrently with or afterthe addition of the bis-phenoxy compounds.

Another facet of the present invention relates to the use of certainmetal compounds with the bis-phenoxy compounds to promote a cooperativeeffect therebetween and thus enhance the flame retardancy of theresultant plastic composition as compared to the flame retardancy ofeither one component used separately. These enhancing agents are fromthe group antimony, arsenic, bismuth, tin and zinc-containing compounds.Without limitation, examples of said enhancing agents include Sb O SbClSbBr SbI AS203, AS205, 211130 BaB O -H O,

and stannous oxide hydrate. The preferred enhancing agent is antimonytrioxide.

The amount of enhancing agent employed in the present inventioncompositions is any amount which when used with said bis-phenoxycompounds will promote a cooperative effect therebetween. In general,the amount employed is from about 1% to about 15%, preferably from about2% to about 10%, by weight, based on the total weight of plasticcomposition. Higher amounts can be used as long as the desired endresult is achieved.

It is also within the scope of the present invention to employ othermaterials in the present invention compositions where one so desires toachieve a particular end result. Such materials include, withoutlimitation, adhesion promotors; antioxidants; antistatic agents;antimicrobials; colorants; flame retardants such as those listed onpages 456-458, Modern Plastics Encyclopedia, ibid., (in addi tion to thenew class of flame retardants described herein); heat stabilizers; lightstabilizers; pigments; plasticizers; preservatives; ultravioletstabilizers and fillers.

In this latter category, i.e. fillers, there can be mentioned withoutlimitation, materials such as glass; carbon; cellulosic fillers (woodflour, cork and shell flour); calcium carbonate (chalk, limestone, andprecipitated calcium carbonate); metal flakes; metallic oxides(aluminum, beryllium oxide and magnesia); metallic powders (aluminum,bronze, lead, stainless steel and zinc); polymers (comminuted polymersand elastomerplastic blends); silica products (diatomaceous earth,novaculite, quartz, sand, tripoli, fumed colloidal silica, silicaaerogel, wet process silica); silicates (asbestos, kaolimite, mica,nepheline syenite, talc, wollastonite, aluminum silicate and calciumsilicate); and inorganic compounds such as barium ferrite, bariumsulfate, molybdenum disulfide and silicon carbide.

The above mentioned materials, including fillers, are more fullydescribed in Modern Plastics Encyclopedia, ibid, and which publicationis incorporated herein (in toto) by reference.

The amount of the above described materials employed in the presentinvention compositions can be any quantity which will not substantiallyadversely effect the desired results derived from the present inventioncompositions. Thus, the amount used can be zero (0) percent, based onthe total Weight of the composition, up to that percent at which thecomposition can still be classified as a plastic. In general, suchamount will be from about 0% to about 75% and specifically from about 1%to about 50%.

The bis-phenoxy compounds can be incorporated into the polyurethanes atany processing stage in order to prepare the present inventioncompositions. In general, this is undertaken prior to fabrication eitherby physical blending or during the process of forming polyurethanes perse. Where one so desires, the bis-phenoxy compounds may be micronizedinto finely divided particles prior to incorporation into thepolyurethanes.

EXAMPLE I Fourteen separate flexible polyurethane foam compositions(designated Nos. 1-14 in Table II) are prepared via the followingprocedure; formulation No. 1 is the control and does not contain abis-phenoxy compound.

Approximately grams polyol (Wyandottes Pluracol GP 3030-a 3,000 mol. wt.triol), 4 grams water, 1.0 grams surfactant (Dow Cornings DC 192asilicone based material), 0.45 grams amine catalyst (Dabco 33 LV-atriethylene diamine based material) and 18 grams (10.0% by weight, basedon the total weight of the foam composition) of each bis-phenoxycompound indicated in Table II are mixed in a paper cup with mechanicalagitation at 1000 r.p.m. for about 10 seconds. Approximately 0.22 (0.19ml.) grams of stannous octoate is added via a syringe to the aboveresultant mixture in the cup. After 5 seconds of agitation,approximately 50 grams (41 ml.) toluene diisocyanate is added via apipet, the mixture agitated for another 5 seconds and then the overallmixture is discharged into a gallon paper container. The foam is thenallowed to rise. After the foam has completely risen, it is allowed toset for about two minutes at 20 C. and then it is post-cured in a forceddraft oven at 220 F. for about 12 minutes. Prior to any testing, thefoam is allowed to set at room temperature (2025 C.) for one week.

Portions of the samples of each respective formulation (Nos. 1-14Table11) prepared according to the above described procedure are thensubjected to two difl erent standard flammability tests, i.e. MVSS No.302 and ASTM D-286370. The Motor Vehicle Safety Standard No. 302 is, ingeneral, the application of a burner to a test specimen (strip) for 15seconds and the timing of the burning for a specified length of thestrip. This procedure is fully set forth in Fire Journal, Vol. 66, No.4, July 1972, pages 34-37 and 44, published by National Fire ProtectionAssociation, Boston, Mass, and which is incorporated herein byreference. ASTM No. D2863-70 is a flammability test which correlates theflammability of a plastic specimen to the available oxygen in itsimmediate environment; this correlation is stated as an Oxygen Index,0.1., level predicated upon the percent oxygen in the gaseous mediumwhich is required to just provide a steady state of continuous burningof the plastic specimen. This ASTM method is fully described in 1971Annual Book of ASTM StandardsPart 27, published by the American SocietyFor Testing and Materials, 1916 Race Street, Philadelphia, Pa.; thispublication is to be considered as incorporated (in toto) herein byreference.

The results of these flammability tests are shown in Table II.

Bis-phenoxy compound Oxygen index, MV SS 302 Formulation number NumberPercent percent (in./min.)

10 17. 8 4. 9 10 22. SE 10 20. 0 1. 4 10 21. 5 SE 21. 1 SE 10 21. 0 SE10 21. 8 SE 10 19. 2 1. 9 10 22. 0 SE 10 19. 8 1. 7 10 21. 7 SE 10 21. 1SE 10 23. 5 SE 10 21. 8 SE Referring to Table II, the bis-phenoxy numberrelates to the structural formulae heretofor set forth in Table I; adifference of 2% in the Oxygen Index values is considered significant;and the MVSS 302 values are set forth in burning rates expressed asinches per minute.

The results shown in Table II demonstrate the unique effectiveness ofthese bis-phenoxy as flame retardants for polyurethanes. Specifically,formulation No. 1 (the control) had an 0.1. of 17.3 and MVSS 302 valueof 4.9. In Nos. 2-14, the use of the particular bis-phenoxy results in asignificant increase in fire retardancy as measured by 01. Furthermore,these formulations also had a reduction in MVSS 302 burning rates and insome cases, the material being tested is found to be self-extinguishing(SE).

EXAMPLE II The use of an enhancing agent such as Sb O to promote acooperative effect between such agent and the bisphenoxy is fullydemonstrated via the results obtained from repeating in full Example Iabove with the exception that 1% Sb O is used in formulation Nos. 214.The 0.1. values are found to be slightly higher than those obtained inExample I. The MVSS 302 rates are found to be basically the same asthose observed in Example I. The

other metal containing enhancing agents are also predicted to beeffective.

EXAMPLE III Samples of each of formulation Nos. 1-14 prepared accordingto the above described procedure of Example I are subjected to thefollowing ASTM test in order to ascertain other properties of theresultant plastic compositions:

ASTM Test No. D-1564 l) Tensile Strength (at break) (2) Density (3)Ultimate Elongation (4) Tear Strength (5) Compression Deflection Theaforementioned ASTM Test is a standard test in the art and is utilizedcollectively in order to ascertain the efficacy of a polymeric system asan overall flame retarded composition for commercial application. ThisASTM Test is to be considered as incorporated herein by reference.

The results of this ASTM test shows that the physical properties of thepresent invention compositions are basically the same (except OJ. andMVSS 302 values) as the plastic material without the flame retardant(i.e. formulation No. 1). Thus, there is no substantial adverse effecton the physical properties of the plastic material when the novelcompounds are incorporated therein.

EXAMPLE IV Samples of each of Formulation Nos. 1 through 14 Table II,are subjected to temperature (thermal) stability tests via the use ofthermal gravimetric analysis (TGA). This test employed the use of aThermal Balance, model TGS-l, Perkin-Elmer Corporation, Norwalk, Conn.and

an electrical balance, Cahn 2580 model, Cahn Instrument Company,Paramount, Calif. The results of these tests show that the bis-phenoxycompound containing Forrnu-. lations had more than adequate stabilityfor melt processing and subsequent heat aging (i.e. high temperatureapplications) and thus demonstrating that the particular bis-phenoxycompound are quite compatible with the plastic material. The bis-phenoxycompound stability thus aids in providing suflicient flame retardancy atthe plastic decomposition temperature. This test also demonstrates thatthese compounds do not exhibit migration.

In view of the foregoing Examples and remarks, it is seen that theplastic compositions, which incorporate these compounds, possesscharacteristics which have been unobtainable in the prior art. Thus, theuse of these compounds in the above described plastic material as flameretardants therefor is quite unique since it is not possible to predictthe effectiveness and functionality of any particular material in anypolymer system until it is actively undergone incorporation therein andthe resultant plastic composition tested according to various AST MStandards. Furthermore, it is necessary, in order to have commercialutility, that the resultant flame retarded plastic composition possesscharacteristics such as being non-toxic. Use of these compounds in theplastic material has accomplished all of these objectives.

The above examples have been described in the foregoing specificationfor the purpose of illustration and not limitation. Many othermodifications and ramifications will naturally suggest themselves tothose skilled in the art based on this disclosure. These are intended tobe comprehended as within the scope of this invention.

I claim:

1. A plastic composition containing polyurethane having incorporatedtherein an effective amount of a flame retardant which is a compoundhaving the formula:

(a) CHr-CH(OH)-CH:

(b) CHr-OH(CHzOH)-GH2 (GH2)r- 2) w where w=16 where X=H, Cl, Br

where S=saturated ring 2. The composition as set forth in claim 1wherein i and i are both 0.

3. The composition as set forth in claim 1 wherein iand i are both 1.

4. The composition as set forth in claim 1 wherein i and i are both 2.

5. The composition as set forth in claim 3 wherein Z is bromine and A iscyano.

6. The composition as set forth in claim 3 wherein Z is bromine and A isnitro.

7. The composition as set forth in claim 3 wherein Z is bromine and A islower alkoxy.

8. The composition as set forth in claim 3 wherein Z is bromine and A islower alkyl.

9. The composition as set forth in claim 3 wherein Z is bromine and A isfluorine.

10. The composition as set forth in claim 3 wherein Z is bromine and Ais dialkylamino.

11. The composition as set forth in claim 3 wherein Z is bromine and Ais phenyl.

12. The composition as set forth in claim 3 wherein Z is bromine and Ais halo-phenyl.

13. The composition as set forth in claim 3 wherein Z is bromine and Ais benzyl.

14. The composition as set forth in claim 3 wherein Z is bromine and Ais halo-benzyl.

References Cited UNITED STATES PATENTS 3,658,634 4/ 1972 Yanagi et a1.161-403 3,717,609 2/1973 Kntner 260-4595 G M. I WELSH, Primary ExaminerUS. Cl. X.R.

260 .75 R, 45.95 G, Dig 24

